Substituted-phenyl-n-alkyl-n-thrihalo-methylthio-carbamates

ABSTRACT

SUBSTITUTED - PHENYL-N-ALKYL-N-TRIHALOMETHYLTHIO-CARBAMATES OF THE GENERAL FORMULA   (X3C-S-N(-R1)-CO-O-),(R3-Y-CH(-Z-R4)-),(R2)N-BENZENE   IN WHOCH X IS CHLORINE, FLUORINE OR BROMINE, N IS 0 OR 2, R1 IS LOWER ALKYL, R2 IS LOWER ALKYL OR ALKOXY HALOGEN OR NITRO, Y AND Z EACH INDEPENDENTLY IS OXYGEN OR SULFUR, AND R3 AND R4 EACH INDEPENDENTLY IS LOWER ALKYL, ALKENYL OR ALKYNYL, OR TOGETHER ARE AN ALKYLENE RADICAL COMPLETING A 5-TO 7-MEMBERED SATURATED HETEROCYCLIC RING OPTIONALLY SUBSTITUTED BY AT LEAST ONE OF LOWER ALKYL OR ALKOXY RADICALS, HALOGEN AND NOTRO, WHICH POSSES INSECTICIDAL, ACARICIDAL AND FUNGICIDAL PROPERTIES.

nited States Patent 3,829,437 SUBSTITUTED-PHENYL-N-ALKYL-N-THRIHALO- METHYLTHIO-CARBAMATES Gerhard Zumach, Cologne, Engelbert Kiihle, Bergisch Gladbach, and Wolfgang Behrenz and Ingeborg Hammann, Cologne, Germany, assignors to Bayer Aktiengesellschaft, Leverknsen, Germany No Drawing. Filed Mar. 14, 1972, Ser. No. 234,663 Claims priority, application Germany, Mar. 19, 1971, P 21 13 454.3 Int. Cl. C07d 13/04, 71/00 US. Cl. 260-327 M 8 Claims ABSTRACT OF THE DISCLOSURE Substituted phenyl-N-alkyl-N-trihalomethylthio-carbamates of the general formula in which X is chlorine, fluorine or bromine, n is 0, 1 or 2, R is lower alkyl, R is lower alkyl or alkoxy, halogen or nitro, Y and Z each independently is oxygen or sulfur, and R and R each independently is lower alkyl, alkenyl or alkynyl, or together are an alkylene radical completing a 5- to 7-membcred saturated heterocyclic ring optionally substituted by at least one of lower alkyl or alkoxy radicals, halogen and nitro,

which possess insecticidal, acaricidal and fungicidal properties.

The present invention relates to and has for its objects the provision of particular new substituted-phenyl-N- alkyl-N-trihalomethylthio-carbamates, e.g. 0-(l,3-dioxolan 2 yl)-phenyl-N-methyl-Ntrihalomethylthio-carbamates, which possess insecticidal, acaricidal and fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids and fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification DOS 1,518,675 that 0 (1,3 dioxolan 2 yl)-phenyl-N- methylcarbamate (Compound A) possesses insecticidal activity.

The present invention provides N-sulfenylated carbamates of the general formula:

in which X is chlorine, fluorine or bromine,

n is 0, l or 2,

R is lower alkyl,

R is lower alkyl or alkoxy, halogen or nitro,

Patented Aug. 13, 1974 pleting a 5- to 7-membered saturated heterocyclic ring optionally substituted by at least one of lower alkyl or alkoxy radicals, halogen and nitro.

These compounds have been found to have strong insecticidal, acaricidal and fungicidal eifectiveness. It is very surprising that the compounds according to the invention show a higher insecticidal, acaricidal and fungicidal potency than the previously known 0-(1,3-dioxolan- 2-yl)-phenyl-N-methylcarbamate. The substances according to the invention therefore represent an enrichment of the art.

Preferably, X is chlorine or fluorine; Y is oxygen; R is methyl; R is methyl, methoxy, chlorine, bromine or nitro; n is 0 or 1; and R and R together are an ethylene, propylene or isopropylene radical, which is linked, as illustrated, to the 0-position of the phenyl ring.

The invention also provides a process for the production of a sulfenylated carbamate of the general formula (I) in which a N-sulfenylated carbamic acid fluoride of the general formula:

R1NC O-F S-CXa (H) is reacted with a phenol of the general formula:

(B2) CH in the presence of an acid acceptor if M is hydrogen, and optionally in the presence of a diluent; in the above-mentioned formulae, R R R R X, Y, Z and n have the meanings indicated above and M is hydrogen or an alkali metal.

If o-(1,3-dioxolan-2-yl)-phenol and N-(fiuorodichloromethylthio)-N-methylcarbamic acid fluoride are used as the starting substances, the course of the reaction can be represented by the following equation:

(IIla) CH: acid-binding agent FC1 CSN-OOF (IIa) sulfenyl chlorides, which are also known, in the presence of a tertiary amine as described in Belgian Patent Specifi-' cation 717,705.

1 The phenols (III) to be used for the reaction are in part known and are open-chain cyclic acetals and mercaptals, the radicals R and R being determined by the monofunctional or polyfunctional alcohols and mercaptans employed in the manufacture of the phenols and identified in more detail below.

the like, with lower alcohols or mercaptans in the presence of acid catalysts such as zinc chloride, mineral acids, p-toluenesulfonic acid and the like. Other acetalizing agents, for example orthoformic acid esters of forminioethers, can also be used for the acetalization, and orthothioborates can, for example, be employed for the mercaptalization. The stoichiometric ratio of the starting products and the functionality of the alcohols or mercapans decide whether open-chain or cyclic acetals or mercaptals are produced.

If the reaction is carried out in two stages, mixed acetals, mercaptals or monothioacetals can be obtained if different alcohols and mercaptans are used.

A further possibility for the preparation of the phenols (III) is the reaction of the corresponding hydroxybenzal chlorides with alcoholates or mercaptides.

-As examples of suitable alcohols and mercaptans for the preparation of the phenols there may be mentioned: methanol, ethanol, propanol, isopropanol, l-butanol, 2- butanol, 2-methyl-1-propanol, allyl alcohol, propargyl alcohol, 2-chloroethanol, 2-bromoethanol, methylmercaptan, ethylmercaptan, n-propylmercaptan, isopropylmercaptan, n-butyl-mercaptan, allylmercaptan, propargylmercaptan, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, 3-methoxy-1-propanol, 3- ethoxy-l-propanol, 3-methoxy-2-propanol, 2-methoxy-1- propanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, 2- methylmercapto-ethanol, 2-ethylmercapto-ethanol, 2-isopropylmercapto-ethanol, 2-methoxy-ethylmercaptan, 2- ethoxyethylmercaptan, 2-isopropoxy-ethylmercaptan, 2- methylmercaptoethylmercaptan, 2 ethylmercapto-ethylmercaptan, ethylene glycol, 1,2-propanediol, 3-fluoro-1,2- propanediol, 3-chloro-1,2-propanediol, 3-bromo-1,2-propanediol, S-methoxy-l,2-propanediol, 3-ethoxy-1,2-propanediol, 3-isopropoxy-1,2-propanediol, 3-allyloxy-1,2- propanediol, 3-methallyloxy-1,2-propanediol, 3-propargyloxy-1,2-propaneidol, 3-acetoxy-1,2-propanediol, 3-methylmercapto-1,2-propanediol, glycerine, 1,3-propanediol, 2- nitro-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- butanediol, 2,3-butanediol, Z-methyl-1,2-propanediol, 3- chloro-Z-chloromethyl-1,2-propanediol, 2-methyl-1,3-propanediol, 2-nitro-2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2- methyl-1,2-butanediol, 2-methyl-l,3-butanediol, 2-methyl- 2,3 butanediol, 2 methyl-2,4-butanediol, 2-methyl-3,4- butanediol, 2-ethyl-1,3-propanediol, 1,4-dichloro-2-methyl- 2,3-butanediol, 4-bromo-2-methyl-2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2,4-hexanediol, 2-methyl-2,3-pentanediol, 3-methyl-2,4-pentanediol, 2,2-dimethyl-3,4-butanediol, 2-ethanol-l-thiol, 2-propanol-1-thiol, 3-chloro-2- propanol-l-thiol, 3-propanol-1-thiol, ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 2,3-butanedithiol, 2,2-dimethyl-1,3-prpanedithiol, and the like. 'Ethylene glycol, 1,3-propanediol, 1,2-propanediol and 2- ethanol-1-thiol are preferentially used.

The aromatic aldehydes required for the manufacture of the phenols of the formula (III) by the method of acetalization or mercaptalization are in part known and can be manufactured according to known methods, e.g. Houben-Weyl, Methoden der Organ. Chemie (Methods of Organic Chemistry), Volume 7, Part 1, Stuttgart, 1954.

As examples of such aldehydes there may be mentioned:

salicylaldehyde, 4-methyl-salicylaldehyde, S-methyl-salicylaldehyde, 4-methoxy-salicylaldehyde, S-methoxy-salicylaldehyde, 4-isopropoxy-salicylaldehyde, 4-chloro-salicylaldehyde, 5-chloro-salicylaldehyde, S-bromo-salicylaldehyde, 4-nitro-salicylaldehyde, S-bromo-salicylaldehyde, 3,5 dichloro salicylaldehyde, 3,5-dibromo-salicylaldehyde, 3,5-dinitro-salicylaldehyde, 3-hydroxy-benzaldehyde, 3-hydroxy-4-methyl-benzaldehyde, 3-hydroxy-5- 4 methyl benzaldehyde, 3 hydroxy-6-methyl-benzaldehyde, 2-chloro-3-hydroxy-benzaldehyde, 4-chloro-3-hy droxy-benzaldehyde, 6-chloro-3-hydroxy-benzaldehyde, 6 bromo 3 hydroxy-benzaldehyde, 3 hydroxy-4- methoxybenzaldehyde, 4-hydr0xy-benzaldehyde, 4-hydroxy-2-methyl benzaldehyde, 4 hydroxy-3-methylbenzaldehyde, 4-hydroxy-3-methoxy-benzaldehyde, 2- chloro-4-hydroxy-benzaldehyde,

and the like. Salicyladehyde is preferentially used.

The reaction according to the invention for the production of the new N-sulfenylated carbamates is preferably carried out in the presence of a solvent, which term in.- cludes a mere diluent. When working with solvents, those which do not react with the N-sulfenylated N-alkylcarbamic acid fluorides, or only react slowly with them, are preferably used. As examples of such solvents there may be mentioned optionally chlorinated hydrocarbons, such as benzene, toluene, methylene chloride, dichloroethane, chloroform, chlorobenzene and dichlorobenzene; ethers, such as diethyl ether, tetrahydrofuran and dioxane; and mixtures of these solvents. Dioxane is preferably used.

In order to bind the hydrogen fluoride produced in the reaction, and acid acceptor, preferably a tertiary base such as triethylamine, or an inorganic base such as an alkali metal hydroxide or alkali metal carbonate, is added to the reaction mixture. It is also possible to start directly from the appropriate alkali metal phenolate and to carry out the reaction in the aqueous phase.

The reaction temperatures can be varied over a wide range. In general the reaction is carried out at about 0 to 100 C., preferably at about 20 to 40 C.

The reactants are usually employed in equirnolar ratios.

The active compounds according to the invention are new and exhibit, with low phytotoxicity, strong insecticidal and acaricidal properties. The active compounds can therefore be used with good results for the control of noxious sucking and biting insects, Diptera and mites (Acarinw). The compounds additionally exhibit a strong fungicidal activity, in particular against soil-borne and seed-borne plant diseases.

For this reason, the new compounds may be used in the crop protection field as Well as in the hygiene field, as insecticides, acaricides and fungicides.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphiaae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi) in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperiaum) as Well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the 'beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix biptinctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neuslria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large White butterfly (Pieris brassicae), the small winter moth (Cheimazobia brum'ata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia Kt'ihniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus lomentosus), the bean weevil (Bruchidius=Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (TribOlium castaneum), the northern corn billbug (Calandm or Sirophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm T enebrz'o moliror) and the saw-toothed grain beetle (Oryzaephilus surinam nsis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (M'elolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as H nschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capimta), the house fly (Musca domestica), the little house fly (Fannia canic- 'ularis) the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus relarzus=Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pil0sus=Pan0nychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsanem us latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithoa'orus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e.. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/ or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum or mineral oil fractions), cycloaliphatic hydrocarbons (e.g. cyclohexane), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.), amines (e.g. ethanolamine, etc.), ethers or esters of such alcohols, ether-alcohols (e.g. glycol monomethyl ether, etc.), methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, strongly polar solvents such as amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/ or with such solid and/or liquid dispersible carrier vehicles and/ or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, rodenticides and fungicides, or bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparation for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably 0.5-% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or filed application generally contemplate those in which the active compound is present in an amount substantially between about 0.000520%, preferably 0.0055% by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0005%, and preferably 0.005-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./hectare, are suflicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids and fungi, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, such fungi, and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally or fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 :L'Dmg test Test insects: Acheta domeslicus (female) Solvent: acetone.

2 parts by weight of the active compound are dissolved mi 1000 parts by volume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 15 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 1:

TABLE 1-Continued LDIOO test Percent Concentration of active compound of the Destruc- Activc compounds solution tion (2).-.- 0 ()CO-NSCGl3 0.2

JJH: 0

(5).". /O ()CO-lTI-SOClzF 0.2 100 L cm (A)-.: O ()COII IH 0.2 40

( CH3 o (known) EXAMPLE 2 LD gg test Test insects: Ornithodorus moubata 3rd-4th nymphal stage Solvent: acetone.

2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 15 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 2:

(known) 9 EXAMPLE 3 LT oo test Test insects: Lasioa'erma serricorne Solvent acetone.

2' parts by weight of active compound are dissolved in '1000'part'sby volume of solvent. The solution so obtained is diluted ,Wllh further solvent to .the desired lower concentrations. y

2.5 ml. of the solution of the active compound are pipettedfinto a Petri dish; On the bottom of the Petri dish there is a' filter paper with a diarneter of about 9.5 cm. ThePetri dish remains uncovered until the solvent has completely eyaporatedjThe" amount of active compound per square meter of filter papervaries with the concentration ofthesolut ionof active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid. 1 The condition ofthe; test insects is continuously observed for up to 72 hours. The time which is necessary for a 100% destruction-is determined.

The test insects, the activecompounds, the concentrations of the active compounds and the periods of time at which there is a 100% destruction-can be seen from the following Table 3:

TABLE 3 LTIOO test Concentration of active compound oithe solution Active compounds inpercent LT 2 o-oo-N-s-c'ol 0.2 4 0 0.04 24 Ha 0.008 72 0.0016 72 (l)...; o O-CO-NSCClzF 0.2 120 I l 0.04 180 I om 0.00s 72 (3).... O O-CO-N-S-CFa 0.2 30

(5)...- 0 O-CO-N-S-CClzF 006i gig CHSI .,-(known). :gr. i

w EXA MPLE 4 LDmo test Test insects: Dermestes peruvianus larvae Solvent: acetone.

2 parts by weight of the active compound are dissolved 'iiYIOOO' pause? vcsuim'epr the solventl The solution so 10 obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of theactive compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 15 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 4:

TABLE 4 LD100 test Percent Concentration active compound of the Destruc- Aetive compounds solution tion 2 O o-o 0NSC on 0.2 100 0. 04 100 H3 (1)-.- O 0-CONS-CC11F 0.2 100 0. 04 100 H3 (3)..- O OCON-SCF5 0.2 100 0. 04 100 CH;

(A)... 0-0 O-NH 0.2 100 O l 0. 04 0 (known) EXAMPLE 5 LD 00 test Test insects: Dermestes peruvianus Solvent: acetone.

2 parts by weight of the active compound are dissolved in 1000 parts bylvolume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of-"the active compound are pipetted into a Petri dish. On the;bottom of the Petri dish there'is a" filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the'solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is cov- A ered with a glass lid.

The condition of the test insects is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds, the testinsects and the resultscan be seen from the following Table 5 f v i TABLE 5 LDIOO test Percent Concentration of active compound of the Destine- Active compounds solution tion (1)- o -CON-S-CC1;F 0.2 100 0. 0i 100 (2).--. O OC0-NSCC1 0.2 100 0. 04 100 H;

(A)..- 0 0-6 0NH-CH1 0.2 100 l 0. 04 0 (known) (B)... 0-0 O--NHCH 0. 2 60 O C H i (known) EXAMPLE 6 Residual test Test insects: Musca domestica and Aedes aegypti Wettable powder base consisting of 3% sodium diisobutylnaphthalene-l-sulfonate 6% sulfite waste liquor, partially condensed with ani- 51% colloidal kaolin;

To produce a suitable preparation-pf the actiye coinpound, 1 part by weight of the active compound. is inti mately mixed with 9 parts byweight of the wettablefpowder base. The spray powder thus obtained is suspended in 90 parts of water. Q j

The suspension of the active compound'is sprayed, in an amount of 1 g. of the active compoundrier'fsqriare meter, on to substrates consisting of "different materials.

The sprayed coatings are, at spcificTinfervals of "time, tested for their biological activity. I.-

For this purpose, theftest insect sf ar'e placed'onlthe treated substrates. There is put over the test insectsja squat cylinder which is closed at.its .upper.end with a wire mesh in order to prevent the insects from escaping. After the insects have spent 8 hours on. the substrate, the de struction of the test insects is determined as a percentage.

The active compounds, the nature of the .testsubstrates and the results can be seen'from Table. 6.

EXAMPLE .7. 1

D rosophila test v To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrateis diluted with water to the desired concentration.

1 cc. of the preparation of the active compound is applied with a pipette to a filter paper disc of Tom. diameter. The wet disc is placed in a glass vessel containing vinegar flies (Drosophila melanogaster) and covered with a glass plate.

After the specified periods of time, the destruction is determined as a percentage: 100% means "that all the flies are killed; 0% means that none of the flies are killed.

The active compounds, their concentrations, the evaluation times and the degree of destruction can be seen from line 45 Table 7.

TABLE 6 Residual test Age of the residual coatings in weeks Active compounds Test substrates Test insects Destruction of the test animals as a percentage (1)-.-- 0 0-0 O-NS-C 0111* Clay limed with Mqaca demeanor-.-" 100 100 100 100 100 100 90 CH 08(OHh. Aedes aegypti 100 100 100 100 100 100 100 100 a v t (B)... 0-0 O-NHCHa ..-:.-do ....r.:..Muaca domestica- 30 .;-r...

Ades ae0ypti...;..... 80 j 50 (known) TABLE 7. Drosophila test (Plant damaging insects) Concentration of Degree of active destruccomtion pound inpereent in after 1 Active compounds percent day (1)..-- O-CO-N-e-S-CClzF 0.2 100 0. 02 90 I I H a o-o o-N s-'o F3 0. 2 100 F) 0 0.02 100 H; 0.002 100 0. 0002 50 0--C O-N-S-C C123 0. 2 100 l 100 CH3 0.002 99 OI- o 0: N,H o. 2 100 0.02 20 EXAMPLE 8 Phaedon larvae test Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 part by weight alkylarylpolyglycol ether.

T o produce a suitable preparation of active compound, 1 part by weight' of the-active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, andthbOncehtrate is diluted with water to the desired concenration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that alL the .heetlelarvaeare killed. 0% means that none of the beetle larvae are killed.

'lh e activjeycompounds,the concentration of the active compound," the times of evaluation and the results can be Concen- Degree of tration of destrucactive tion in compercent pound in after 3 Active compounds percent days,

(2)...- O 000-N-so0n 0.2 1 o. 02 100 H; 0.002 00 (4)-.-- o 0-0 0-N-S-C Ch 0.2 100 C T a 0. 02 100 0.002 70 (3) O 0c0-N-s-C F; 0.2 100 1 0. 02 100 Ha o. 002 100 (5)...- O o-o 0N S'-C 0hr 0 g I 0H1 0.002 7o (6) s 0-CONS 00111 0.2 100 A 0; 02 100 (B)-.- 0-0 0- N-H 0. 2 10 J 0. 02 20 Ha (CHa)zCH-O (known) EXAMPLE 9 Tetranychus test/resistant Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 part by weight alkylaryl polyglycol ether.

Bean plants (Phaseolus vulgaris), which have a height of approximately 1030 cm., are sprayed, with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentages 100% means that all the spider mites are killed Whereas 0% means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table '9:

TABLE 9 Tetranyehus test (resistant) (Plant damaging mites) Active compounds Degree of destruction in percent after 3 days (known) (known) Mycelium growth test-Active compounds (1).... O-0 0N-SO C111? II C Concentration of active compound,

p.p.m.

16 EXAMPLE 10 Mycelium' growth test Nutrient medium used: 7

20 parts by weight agar-agar 200 parts by Weight potato decoction 5 parts by weight malt 15 parts by weight dextrose 5 parts by weight peptone. I

2 parts by weight Na HPO 0.3 part by weight Ca(NO Proportion of solvent to nutrient medium:

2 parts by weight solvent mixture parts by weight agar nutrient medium Composition solvent mixture 0.19 part by weight DMF 0.01 part by weight emulsifier EmulvinW 1.80 parts by weight water Proportion of solvent to nutrient medium:

2 parts by weight solvent mixture v 100 parts by weight agar nutrient meduim.

The amount of active compound required for the de I sired concentration of active compound in the nutrient medium is mixed with the stated amount of solvent. The concentrate is thoroughly mixed in the stated proportion with the liquid nutrient medium which'has been cooled to 42 C. and is then poured into Betti dishes of 9 cm. diameter. Control dishes to which the preparation hasn'ot been 0=no fungus growth 1-=very strong inhibition of growth 2:medium inhibition of growth 3=slight inhibition of growth 4=growth equal to that of untreated control.

The active compounds, their concentrations and the re sults obtained can be seen from Table 10: t

TABLE 10 Fungi Cochliobolus 1n izlabea'nua Phialophora cinerescms v Colleto trichum eojfeanu'm M1100- ephaerella v musicola Pellicu- Zaria easalcii 17 EXAMPLE ll Piricularia test: liquid preparation of active compound Solvent: 1.9 parts by weight DMF Dispersing agent: 0.1 part by weight emulsifier Emulvin W The test insects, the active compounds, theconcentrations of the active compounds and the periods of time at which there is a 100% destruction can be seen from the following Table 12:

T BLE 12 Water: 98 parts by weight water. LTm 2 for mm" The amount of active compound required for the de- """'C gnr"-""- sired concentration in the spray liquor is mixed with the f il stated amount of solvent, and the concentrate is diluted coinfifidfig with the stated amount of water containing the stated disg fgg pegsng ageillt. b 14 d 1d -d h th Active compounds npercent LTm rice p ants a out ays o are spraye wit e sPray liquor until dripping wet. The plants remain in a O CO I seek 0962 i? greenhouse at temperatures of 22 to 24 C., and a relative L008 atmospheric humidity of about 70% until they are dry.

They are then inoculated with an aqueous suspension of 0 100,000 to 200,000 spores/ml. of Piricularia oryzae and placed in a chamber at 24-26 C. and 100% relative atmospheric humidity. 0 O-OON SQCIBF 5 days after inoculation, the infection of all the leaves 3 90 I present at the time of inoculation is determined as a percentage of the untreated but also inoculated control plants. 0 0% means no infection; 100% means that the infection is exactly as great in the case of the control plants. 25

The active compounds, the concentrations of the active Q2 compounds and the results can be seen from the following 0 B 04 Table 11: 958 i 21,

TABLE 11 1 Piricularia test/liquid preparation of active compound 30 0 Infection a? 31 pin- (2 D fe cti i l o the uii- 0 62 83: treated control CH; with a concentraa tion of active compound (in percent) Active compound ot- 0 E 065? 3 o o-oo-Ns-oo1iF 5 0 o-oo-rt-s-rmnr 0.2 45' CH: H:

E 096 22 1% (A)... O 0-CO-N-H 0.2 90' CHa-NH- S 5H 0.04 105' /Zn m-un-o-s 0 (known) (known) EXAMPLE 12 EXAMPLE 13 LT test for Diptera LT test for Diptera Test insects: Musca domestica Solvent: acetone.

4 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid. I

The condition of the test insects is continuously observed. The time which is necessary for a 100% destruction is determined.

Test insects: Aedes aegypti Solvent: acetone.

2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 2 5.tes't insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed. The time which is neeessary for a destruction is determined.

TABLE 13 LTm test for Diptera Concentration of active compound 01' the solution Active compounds in percent OC ONS 012B O-CO-N-S-C Fl 0-0 ON- S-C Ola CHa- O 5 (known) Norm-In this and other tables, 8 =95% means that after 8 hours there is a 95% destruction of the test animals.

EXAMPLE 14 LTmo test Test insects: Tribolium confusum Solvent: acetone.

2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petri dish. 0n the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed for up to 72 hours. The time which is necessary for a 100% destruction is determined.

The .test insects, the active compounds, the concentrations. of the active compounds and the periods of time at which there is a destruction the following Table 14:

can be seen from TABLE 14 LTmo test Concentration of active compound of the solution Active compounds in percent LTIOO 2). 0 0-0 ONS-C C1, 0. 2 180 1)- 0 0-0 ONS-C ChF 0. 2 45' 3 OC ONS-CF 0. 2 15' 0 o. 04 60 0. 008 72 (5).. OC 0NSC Ch 0. 2

orn 4 (4)-. o 0-0 ONS-C Ch 0. 2 72 CHzl 0. 04 72 CHI (A)... 0 0-0 ONH 0. 2 72 (known) The following further examples are set forth to illustrate, without limitation, the process for producing the active compounds according to the present invention.

EXAMPLE 15 OH; O

33 g. of o-(1,3-dioxolan-2-yl)-phenol (0.2 mole) and 48 g. of N (fiuorodichloromethylthio) N methyl-carbamic acid fluoride (0.23 mole) are dissolved in 300 ml. of dioxane. 20.5 g. of triethylamine are added dropwise to this solution at room temperature. When the weakly exothermic reaction has subsided, the mixture is stirred for 1 hour at room temperature and subsequently for 30 minutes at 60-70 C., and is cooled and poured into 700 ml. of ice water. The oil which precipitates is taken up in methylene chloride and washed with water. After drying the solution and evaporating otf the methylene chloride, distillation yields 57 g. of the above compound, of boiling point 162164 (0.13 mm. Hg) as a yellowishcolored oil which crystallizes on standing. Melting point 50-51 (petroleum ether), colorless crystals.

21 EXAMPLES 16-20 The following compounds are obtained analogously to Example 15:

11: -0 0-N-S-C Cl:

(2).... Melting point:

EXAMPLE 21 35 g. of N (flurodichloromethylthio) N methylcarbamic acid fluoride (0.165 mole), dissolved in 30 ml. of dioxane, are added dropwise, at -l5, to a sodium 0-(l,3-dioxan-2-yl) phenolate solution which has been prepared from 27 g. of 0-(l,3-dioxan-2-yl)-phenol (0.15 mole), 6 g. of sodium hydroxide and 300 ml. of water. The mixture is stirred for 1 hour at room temperature, the resulting oil is taken up in methylene chloride and the organic phase is twice washed with water, dried and evaporated. The residual oil is completely freed of the solvent in a high vacuum at 70-80" C. bath temperature. 61 g. of the above compound are obtained as a yellowbrown oil 'which crystallizes on standing. Melting point 6566 C. (petroleum ether).

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

22 What is claimed'is: 1. An N-sulfenylated carbamate of the formula OCO--NSCX:

in which X is chlorine, fluorine or bromine,

Y and Z each independently is oxygen or sulfur, and

R is ethylene, propylene or isopropylene.

2. The compound according to claim 1 wherein such compound is o-(l,3-dioxolan-2-yl) phenyl N methyl- N-fluorodichloromethylthio-carbamate of the formula 3. The compound according to claim 1 wherein such compound is o-(l,3-dioxolan-2-yl)-phenyl N methyl- N-trichloromethylthio-carbamate of the formula CIHa 0-0 O-N-S-CCh 4. The compound according to claim 1 wherein such compound is 0-(1,3-dioxolan-2-yl) phenyl N methyl- N-trifluoromethylthio-carbamatc of the formula O-GO-IL-S-CF:

5. The compound according to claim 1 wherein such compound is 0- [4-methyl-(1,3-dioxolan-2-yl)] phenyl- N-methyl N trichlorornethylthio-carbamate of the formula 7. The compound according to claim I wherein such compound is 0-(l,3 thia-oxolan. 2 yl) phenyl N- 23 methyl N fluorodichlormethylthio-carbamate of --the formula ---S Lo 24 References Cited- UNITED S TATE S P ATI INTS Jones et a1. '1'67--22 7/1961 Jacobi ct a1 l6730 10/ 1967 Wcil, 260-479 3/1972 Wail 260-479 5/1972 Brown et a1. 260470 FOREIGN PATENTS 10/1966 France 260340.9 11/1970 Germany 260-479 HENRY R. JILES, Primary Examiner 15 C. M. S. JAISLE, Assistant Examiner US. Cl. XQR.

71-88, 90, 98; 260-338, 340.7, 340.9, 479 c; 424- 273, 276, 278, 300 l I 5,829, 57 August 15, 197

Patent No. Dated Inventor) Gerhard Zumach et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

-Co1. l, in the Title, change "I H RIH. ALO-"' t o 1"RlllALO -l 'Col. 1, compound (1) line 61, correctformula to-read as follows: v R I 0-0 o-1 :-s-c x.

ColfZ, line .68, after "open-chain" insert or Col. 3, line 41, correct spelling of "propanediol",

first occurrence.

Col. 3 line 72 chang e "5 ;-bromo" to 5 -nitr'o Col. 4, line 23, change "and" to an Col. 6, line 50, correct spelling of "field";

Col. 13, line 49, correct spelling of "concentration".

Col. 14, Table 8, Compound (4), at beginning of formula, cancel "0" an; substitute CH FORM PO-10SO (10-69) USCOMM'DC 60376-P69 v.5, covlRNMzNT PRINTING OFFICE: 859- 93 o z I Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. Dated g t 3 974 In entor( It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. line 7,, Table 9, heading of last column of Table,

- change "3" to 2 Col. 16, line 22, correct spelling of "medium".

Signed and sealed this 17th day of December 1974.

(SEAL) Attest:

ZicCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-DSO (YD-69)- USCOMM-DC 60376-P69 u,s. covmunzm PRINTING omci: 59. 93 Q 

